A novel process for the direct ammoxidation of propane over steam-activated Fe-silicalite at 723-823 K is reported. Yields of acrylonitrile (ACN) and acetonitrile (AcCN) below 5% were obtained using N2O or O-2 as the oxidant. Co-feeding N2O and O-2 boosts the performance of Fe-silicalite compared to the individual oxidants, leading to AcCN yields of 14% and ACN yields of 11% (propane conversions of 40% and products selectivity of 25-30%). The beneficial effect of O-2 on the propane ammoxidation with N2O contrasts with other N2O-mediated selective oxidations over iron-containing zeolites (e.g. hydroxylation of benzene and oxidative dehydrogenation of propane), where a small amount of O-2 in the feed dramatically reduces the selectivity to the desired product. It is shown that the productivity of ACN and especially AcCN, expressed as mol product h(-1) kg(cat)(-1) , is significantly higher over Fe-silicalite than over active propane ammoxidation catalysts reported in the literature. Our results open new perspectives to improve the performance of alkane ammoxidation catalysts.